AU2008299587A1 - Limonite and saprolite heap leach process - Google Patents
Limonite and saprolite heap leach process Download PDFInfo
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- AU2008299587A1 AU2008299587A1 AU2008299587A AU2008299587A AU2008299587A1 AU 2008299587 A1 AU2008299587 A1 AU 2008299587A1 AU 2008299587 A AU2008299587 A AU 2008299587A AU 2008299587 A AU2008299587 A AU 2008299587A AU 2008299587 A1 AU2008299587 A1 AU 2008299587A1
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- Australia
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- ore
- process according
- heap
- nickel
- limonitic
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- 238000000034 method Methods 0.000 title claims description 49
- 230000008569 process Effects 0.000 title claims description 48
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 124
- 229910052759 nickel Inorganic materials 0.000 claims description 58
- 239000002253 acid Substances 0.000 claims description 30
- 238000002386 leaching Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 27
- 229910017052 cobalt Inorganic materials 0.000 claims description 23
- 239000010941 cobalt Substances 0.000 claims description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 16
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 13
- 239000011707 mineral Substances 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 11
- 230000007704 transition Effects 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005363 electrowinning Methods 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000000638 solvent extraction Methods 0.000 claims description 4
- 239000013535 sea water Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000013505 freshwater Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000005486 sulfidation Methods 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims 3
- 150000004679 hydroxides Chemical class 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 24
- 238000012360 testing method Methods 0.000 description 23
- 239000002131 composite material Substances 0.000 description 22
- 229910052598 goethite Inorganic materials 0.000 description 16
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 16
- 229910001710 laterite Inorganic materials 0.000 description 16
- 239000011504 laterite Substances 0.000 description 16
- 238000000605 extraction Methods 0.000 description 11
- 239000011019 hematite Substances 0.000 description 10
- 229910052595 hematite Inorganic materials 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 10
- 238000005054 agglomeration Methods 0.000 description 8
- 230000002776 aggregation Effects 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000004927 clay Substances 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 230000002262 irrigation Effects 0.000 description 5
- 238000003973 irrigation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000012527 feed solution Substances 0.000 description 4
- 229910000273 nontronite Inorganic materials 0.000 description 4
- 229910052596 spinel Inorganic materials 0.000 description 4
- 239000011029 spinel Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 241000080590 Niso Species 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 238000009853 pyrometallurgy Methods 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910021647 smectite Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000004125 X-ray microanalysis Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052899 lizardite Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- IBPRKWGSNXMCOI-UHFFFAOYSA-N trimagnesium;disilicate;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IBPRKWGSNXMCOI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/242—Binding; Briquetting ; Granulating with binders
- C22B1/243—Binding; Briquetting ; Granulating with binders inorganic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
WO 2009/033227 PCT/AU2008/001357 LIMONITE AND SAPROLITE HEAP LEACH PROCESS This invention relates to the hydrometallurgical process for the recovery of 5 nickel from oxide ores, in particular the heap leaching of lateritic ores that include both saprolitic and limonitic components. Background of the Invention Laterite ores are potentially the world's largest source of nickel and cobalt. In 10 general, most deposits of nickel/cobalt laterites contain three major zones based on morphology, mineralogy and chemical composition. These three zones, from the base to the surface, atop weathered parent bedrock materials are the saprolite zone, the transition zone and the limonite zone. There is generally a large variation in total thickness of the laterite deposit, as well as 15 individual zone thickness. The saprolite zone consists predominantly of "saprolitic serpentine" minerals and a large variety of nickel/magnesium silicate minerals. The weathering process, or "serpentinization" of the parent bedrock material is characterised 20 by a decrease in the magnesium content and an increase in the iron content of the top layer of ore body. The resulting saprolite zone contains between 0.5% and 4% nickel and a higher magnesium content, which is normally over 6%wt. The not well defined transition zone is composed essentially of limonite and 25 saprolite. It also commonly contains nickel in the range of from 1.0% to 3.0% with co-existing cobalt ranging from 0.08% up to 1% (associated with asbolane, a hydrated manganese oxide). The limonite zone, located on the top zone of lateritic ore body, contains nickel 30 ranging from about 0.5% to 1.8% and consists of goethite-rich and/or hematite rich ore, which is rich in iron and cobalt. It has a lower magnesium content than saprolitic type ore. Due to stronger weathering, limonitic ore contains dominantly fine and soft particles of goethite and/or hematite. Sometimes the weathering has not been fully completed and either the hematite or the WO 2009/033227 PCT/AU2008/001357 -2 goethite rich sections are not present. Alternatively, depending upon the climatic condition, the limonite zone will still contain residual iron/aluminium silicates, such as nickel-containing smectite, nontronite and chlorite. At atmospheric pressure and ambient temperature, the acidic leach of limonite is 5 slow. The whole-ore dissolution reaction using sulfuric acid is shown as follows: Limonite leach (Fe,Ni)O.OH + H 2
SO
4 -> NiSO 4 + Fe.
3 + SO4 2 + H 2 0 Eq. 1 Goethite 10 (Fe,Ni) 2 0 3 + H 2
SO
4 -> NiSO 4 + Fe.
3 + SO4 2 + H 2 0 Eq. 2 Hematite The iron content of limonite ore is normally in the range of 25-45%wt which 15 corresponds to 40-72%wt goethite (FeOOH) or 36-64%wt hematite (Fe 2
O
3 ). Consequently the dissolution of Ni-containing goethite or hematite of a limonitic heap causes the instability of a heap, such as severe volumic slumping or shrinkage, and poor irrigation permeability. 20 The less-weathered, coarse, siliceous and higher nickel content saprolites tend to be commercially treated by a pyrometallurgical process involving roasting and electrical smelting techniques to produce ferro nickel. The power requirements and high iron to nickel ore ratio for the lower nickel content limonite blends make this processing route too expensive. Limonite ores are 25 normally commercially treated by a combination of pyrometallurgical and hydrometallurgical processes, such as the High Pressure Acid Leach (HPAL) process, or the reduction roast - ammonium carbonate leach process. Acid leaching of saprolitic ore is not practised commercially for the reason that 30 a process has not been developed for recovering the nickel from the leach solution in an economical and simple manner. While heap leaching copper ores is well known as a commercial operation, there are several differences between heap leaching of copper containing ores WO 2009/033227 PCT/AU2008/001357 -3 that also contain some clay components, and the lateritic ores that have substantial fine and/or clay components. In addition, the acid consumption of laterite ore is ten-fold that of heap leaching copper ores. 5 It has been found that the permeability of lateritic ore is largely controlled by the type of mineral occurrence, mineral morphology and particle size. Although the mineralogy of lateritic ore is rather complex and widely variable from deposit to deposit, there is some commonality or similarity of mineral morphology in the worldwide lateritic nickel deposits. These morphological 10 structures enhance permeability of solution and preserve physical stability of individual minerals. Heap leaching of nickeliferous oxidic ore has been proposed in recovery processes for nickel and cobalt and is described, for example in U.S. Patents 15 5,571,308 and 6,312,500, both in the name of BHP Minerals International Inc. U.S. Patent 5,571,308 describes a process for heap leaching of high magnesium containing laterite ore such as saprolite. The patent points out that the fine saprolite exhibits poor permeability, and as a solution to this, 20 pelletisation or agglomeration of the ore is necessary to ensure distribution of the leach solution through the heap. U.S. Patent 6,312,500 also describes a process for heap leaching of laterites to recover nickel, which is particularly effective for ores that have a significant 25 clay component (greater than 10% by weight). This process includes sizing of the ore where necessary, forming pellets by contacting the ore with a lixiviant, and agglomerating. The pellets are formed into a heap and leached with sulfuric acid to extract the metal values. Sulfuric acid fortified seawater may be used as the leach solution. 30 International application PCT/AU2006/000606 (in the name of BHP Billiton SSM Technology Pty Ltd) also describes a process where nickeliferous oxidic ore is heap leached using an acid supplemented hypersaline water as the WO 2009/033227 PCT/AU2008/001357 -4 lixiviant with a total dissolved solids concentration greater than 30 g/L in order to leach the heap. Heap leaching laterites offers the promise of a low capital cost process, 5 eliminating the need for expensive and high maintenance, high pressure equipment required for conventional high pressure acid leach processes. These patents and applications exclude the processing of limonitic laterite for heap leach because, in addition to the low reactivity, the reaction mechanism of whole-ore dissolution shown in Eq.1 and 2 may lead to the collapse and/or 10 poor permeability of the heap due to the dissolution of nickel containing goethite or hematite as outlined above. Each of these patents/applications does not claim to explore the whole ore body or the fraction of an ore body such as transition zone, which contain 15 considerable limonite and saprolite. Most heap work testing to date has been conducted with large components of the heap comprising the coarser saprolitic component of a laterite ore. One problem hindering the heap leaching of nickel and cobalt containing 20 nickeliferous oxidic ores is the substantial clay or fine-particle component of such ores, particularly ores which contain significant quantity of limonitic type ores. The type of clay content is dependent on the parent rock and the physicochemical environment of the clay formation, but most clays have a detrimental effect on the percolation of the leach solution through the ore. 25 The present invention aims to develop a process where a heap comprising at least a significant proportion of both limonitic and saprolitic type ore components can be placed in a heap and subjected to heap leaching. 30 A reference herein to a patent document or other matter which is given as prior art is not to be taken as an admission that that document or matter was known or that the information it contains was part of the common general knowledge as at the priority date of any of the claims.
WO 2009/033227 PCT/AU2008/001357 -5 Brief Description of the Invention The applicants have developed a process where a transition zone ore of a laterite ore body and/or the mixed blend of both limonite and saprolite ore may 5 be heap leached without the associated difficulties, such as collapse and/or poor irrigation permeability of the heap, which may generally be expected when heap leaching a heap with a significant limonite content. The process of the invention includes the step of maintaining a sufficient proportion of both limonite and saprolite within the heap to maintain the integrity of the heap. 10 Accordingly, the present invention provides a process for the recovery of nickel and/or cobalt from a lateritic ore by heap leaching, the process including the steps of: 15 a) forming one or more heaps from a lateritic ore body wherein that lateritic ore body includes a blend of both limonitic and saprolitic type ores; b) leaching the ore heap with a leach solution; and c) recovering the nickel and/or cobalt from the resultant heap leachate. 20 The inventors have surprisingly found the outline shape of reacted saprolite or leaching residue during an acidic leach of a saprolite type ore was not changed due to the formation of SiO 2 (Quartz). The reaction of acidic leach of saprolite showing the formation of quartz is shown in Eq, 3. 25 Saprolite Leach: (Mg,Ni,) 2
-
3 Si 2 0 5
(OH)
4 + H 2
SO
4 -> Mg.
2 + Ni.
2 + SO4 2 + SiO 2 + H 2 0 Eg.3 Serpentine 30 The mechanism could be described with "Shrinking Core Model" (SCM) with porous solid product (quartz) formation as shown in the photo of Figure 1. The formation of acid-resistant quartz can act as a "backbone" within the agglomerated pellets and can strengthen and stabilize a heap that includes limonite.
WO 2009/033227 PCT/AU2008/001357 -6 Consequently, the inventors have found that a heap charged with lateritic ore may be stable during acidic leach if the ratio of saprolite/limonite type ores is appropriately selected. In one embodiment, the inventors have found that a 5 stable heap may be maintained if the limonite/saprolite blended heap includes 15%-85% wt of limonitic type ore and 15%-85% wt of saprolitic type ore. Preferably the blend will include 40%-60% wt of limonitic type ore and 40% 60% wt of saprolitic type ore. The process of the invention is aimed at processing a blend of limonitic and saprolitic ore types, and includes transition 10 zone ore where the limonite and saprolite components are already naturally blended. It also includes processing limonite and saprolite blends where the limonite and saprolite has been sourced individually from limonitic, saprolitic and/or transition zones. 15 Preferably the limonitic type ore to saprolitic type ore weight ratio in the blend within the heap will be anywhere from 5:1 to 1:5, but most preferably about 1:1. Further, the overall silicon content of the blended ore is preferably greater than 13% wt silicon, and more preferably within the range of 15% to 40% wt silicon. The blended limonite and saprolite preferably has a quartz content 20 greater than 28% wt, more preferably, the blend will have a quartz content in the range of from 32% to 86% wt. An advantage of the process of the present invention is that the run of mine ore may be used without post mining separation and/or classification, which 25 includes directly processing transition type ore. This leads to exploration efficiencies as the whole of ore may be subjected to heap leaching. In the process of the invention, the heap is subjected to a leach process by contacting a heap of the ore with a mineral acid selected from the group 30 consisting of hydrochloric acid, sulfuric acid and/or nitric acid at an acid concentration sufficient to effect the dissolution of nickel, for example, at least about 0.1 molar (equals to 10 g/L H 2
SO
4 ). Preferably sulfuric acid is used. The aqueous leach solution may be acid supplemented fresh water, seawater or saline water.
WO 2009/033227 PCT/AU2008/001357 -7 The leaching is preferably carried out at a temperature of at least ambient temperature and ranging up to about 800C, if additional exothermic reaction such as bio-oxidation is introduced. The reaction time should be sufficient to 5 dissolve substantial amounts of nickel and some iron and magnesium to provide a pregnant solution thereof. The limonite ore generally consists of goethite and/or hematite type particles and is particularly fine and dissolved with acid as shown in Eq. 1 and 2. The 10 saprolite ore is coarse silicates which volume was found unchanged during leach as shown in Eq.3 and the photo (Figure 1). Accordingly there needs to be a certain quantity of saprolitic type ore within the heap in order to give the heap some structure backbone during the leaching phase. The applicants have found that it is still possible to leach a blend of limonite and saprolite ore 15 within a heap with as little as 15%wt of the heap comprising saprolitic type ores, and the blended material containing greater than 13% silicon, preferably in the range of from about 15% to about 40% silicon. It is preferred to agglomerate or pelletize the particles prior to leaching in order 20 to maintain high percolation flux to provide accelerated heap leaching kinetics. Further, pelletisation also enables for control of the iron inside the heap and decreases acid consumption by making larger particles from the fine particles. In order to agglomerate the ore, a nickel containing lateritic ore may be 25 crushed so that the particles are less than 2.5cm. The particles may then be agglomerated or pelletized by mixing the crushed lateritic ore particles with a concentrated acid, for example, in a rotary disk, drum or other suitable apparatus. Concentrated sulfuric acid is a preferred acid. The amount of acid used to agglomerate the pellets is generally that amount required to initially 30 attack the nickel containing mineral matrix. In general, the amount of acid ranges from about 10kg to about 125kg of acid per tonne of ore, depending on the ore characteristics such as saprolite or limonite or smectite/nontronite/chlorite.
WO 2009/033227 PCT/AU2008/001357 -8 The pellets are then formed into a heap having a base and a top. A leach solution is applied to the top of the heap and allowed to percolate downward through the heap. The leach solution is collected at the bottom and may be recycled, or collected for nickel and/or cobalt recovery. 5 Preferably, a plurality of heaps is formed and arranged in at least a primary and secondary heap, the process including the steps of: a) adding the leach solution to the secondary heap to produce an intermediate pregnant leachate solution; and 10 b) adding at least a part of the intermediate pregnant leachate solution to the primary heap to leach the primary heap in a counter current process, and producing a nickel and cobalt rich heap leachate for further nickel and/or cobalt recovery. 15 The intermediate pregnant leachate solution is rich in nickel and cobalt with low acidity, but also contains iron and a number of other impurities. The counter current heap leach process has the advantage of lowering acid consumption, and also achieves lower iron concentration and higher nickel concentration in the pregnant leachate solution and results in a cleaner 20 product liquor of lower acidity than the single heap system. The intermediate pregnant leachate solution may be divided into two fractions with the fraction having a pH of greater than 2 being removed and transferred downstream for nickel and/or cobalt recovery. The acidic fraction with a pH of 25 less than 2 may be used for the leach solution in the counter current system. The nickel and cobalt rich heap leachate may be divided in a similar manner with the fraction having a pH greater than 2 being transferred for nickel and cobalt recovery, while the acidic heap leachate with a pH of less than 2 is used to leach a fresh heap in the counter current process. 30 The nickel and/or cobalt recovery may include ion exchange (IX), solvent extraction (SX), electrowinning (EW), multi-stage neutralisation to produce Ni/Co hydroxide, pyrohydrolysis to produce Ni/Co oxides and sulfidation to produce Ni/Co sulfides.
WO 2009/033227 PCT/AU2008/001357 -9 Brief Description of the Drawings The figures of the accompanying drawings illustrate aspects of 5 particular preferred embodiments of the present invention, wherein: Figure 1 a porous solid product (quartz) formation used in an ore heap of one embodiment of the process according to the present invention. 10 Figure 2 shows progressive nickel extraction graphs of blended ores Nos. 1 to 3 for example 5. Examples 15 Example 1: Mineralogy of the Blended Composite Ore The blended ore sample taken from the same deposit for tests of Examples 2 to 4 was lightly ground using a mortar and pestle to separate aggregated grains, loaded into a stainless steel sample holders and analysed by XRD 20 using the Scintag X'Tra diffractometer scanning between 2 and 80 degrees 2 theta with CuKapha radiation. Polished sections of each sample were coated with around 40 nanometres of carbon and examined by scanning electron microscopy (SEM) and energy dispersive X-ray microanalysis (EDS) to obtain elemental compositions of individual minerals and determine speciation and 25 distribution of nickel and cobalt. The results shown in Table 1 indicate that there were considerable existence of limonite and saprolite in the blended ore, classified with characteristic mineral goethite and serpentine respectively. 30 35 WO 2009/033227 PCT/AU2008/001357 -10 Table 1: Mineralogy of the Blended Composite Ore Sample No. Mineralogy Nickel Distribution XRD showed major quartz with Nickel is distributed widely in this ore, MT3124-3127 moderate goethite, low with the highest concentrations found in serpentine and low hematite. the very rare areas of asbolane. Lesser Detailed SEM/EDS identified but still significant amounts of nickel were small amounts of chromite, detected in the moderately abundant spinel, nontronite and Ni-rich serpentine and less common nontronite, asbolane. There was no with the abundant goethite/limonite identifiable difference in showing very sporadic nickel content mineralogy between drums using varying from zero to 3%NiO. Widely XRD. EDS batch analyses of scattered grains of spinel and magnetite individual grains in each drum also contain some nickel. Note that not all sample showed no significant serpentine and goethite grains contain differences in mineral detectable nickel. Many of the goethite composition between drums. grains that contain nickel also contain Goethite occurs as both dense appreciable amounts of chromium and limonitic material and quartz occurs mainly as free grains in all size ranges. This ore appears to be intermediate between saponite wt h budnoand limonite.ethite/limonite 5 Example 2: Single-pass Column Leaching and Counter-current Column Leach without Acid Dose during Agglomeration The laterite ore used for these tests were the blended composite ore with limonite/saprolite weight ratio of around 1:1. Table 2 illustrates the chemical 10 composition of the composite ore. Table 2: Chemical Composition of Blended Laterite with Limonite/Saprolite Weight Ratio of 1:1 Al Co Cr Fe Mg Mn Ni Si Coieosite 1 2.28 0.08 1.64 31.28 6.16 0.95 1.38 14.29 Composite 2 i2.13 i0.07 1.03 28.00 9.71 0.50 1.30 14.29 Avera e 2.20 0.08 1.34 29.64 7.93 0.73 1.34 14.29 15 No sulfuric acid was used during agglomeration as the ore contained clay marked by aluminium, which acted as a binding material for agglomeration. The agglomerated laterite was charged into two columns BCre and BC02 with size of D x H = 160cm x 400 cm. In a single-pass style test, the blank sulfuric solution with constant acidity of around 100 gL was fed into column Be.1 to 20 produce a PLS (pregnant leachate solution). The PLS fraction with pH>2 was directly transferred to downstream for nickel recovery. The acidic PLS fraction with pH<2 was transferred to column B02 filled with freshly agglomerated ore WO 2009/033227 PCT/AU2008/001357 - 11 for counter-current leach. After the nickel extraction of BC01 approaching the targeted extraction and shut down, the feed solution to BC02 was switched to the blank sulfuric acid with acidity of around 100 g/L. The treatment of the PLS of Column BC02 was the same as Column BC01: transfer the PLS fraction 5 with pH>2 to nickel recovery section and transfer the acidic PLS fraction with pH<2 as feed solution for next column. The test conditions and results are listed in Table 3. Table 3: Test Conditions and Results Column Operation Ore Irrigation Test Slump Acid Extraction % Style charge Flux Day % Consumption Ni Co Fe (kg) (L/m 2 /hr) (kg/t ore) BC01 Single 9591 11 124 20 672 61 77 40 Pass BC02 Counter 11989 10 262 16 322 51 37 17 Current 10 Example 3: Single-pass Column Leaching and Counter-current Column Leach with Acid Dose during Agglomeration The laterite ore used for these tests were the blended composite ore with limonite/saprolite weight ratio of 1:1. Table 4 illustrated the chemical 15 composition of the composite ore. Table 4: Chemical Composition of Blended Laterite with Limonite/Saprolite Weight Ratio of 1:1 Al Co Cr Fe Mg Mn Ni Si Composite 8 2.41 0.09 1.51 29.94 5.44 1.04 1.42 18.31 | Composite 7 2.49 0.07 1.27 26.62 6.32 0.53 1.32 15.18 Average 2.45 0.08 1.39 28.28 5.88 0.79 1.37 16.74 20 Concentrated sulfuric acid was used during agglomeration. The agglomerated laterite was charged into two columns BC08 and BC07 with size of D x H = 160cm x 400 cm. In a single-pass style test, the blank sulfuric solution with constant acidity of around 75 g/L was fed into column BC08 to produce a PLS (pregnant leachate solution). The PLS fraction with pH>2 was directly 25 transferred to downstream for nickel recovery. The acidic PLS fraction with pH<2 was transferred to another column BC07 filled with freshly agglomerated ore for counter-current leach. After the nickel extraction of BC08 approaching WO 2009/033227 PCT/AU2008/001357 -12 the targeted extraction and shut down, the feed solution to BC07 was switched to the blank sulfuric acid with acidity of around 75 g/L. The treatment of PLS of Column BC07 was the same as Column B08: transfer the PLS fraction with pH>2 to nickel recovery section and transfer the acidic PLS fraction with pH<2 5 as feed solution for next column. The test conditions and results are listed in Table 5. Table 5: Test Conditions and Results Column Operation Ore Agglomer- Irrigation Test Slump Acid Extraction % Style charge ation acid Flux Day % Consump Ni Co Fe (kg) dose (kg/t (L/m 2 /hr) tion ore) (kg/t ore) BC08 Single 10186 52 11 150 21 608 68.8 79.2 30.4 Pass BC07 Counter 11334 89 10 259 11 330 53.0 80.1 13.2 Current 10 Example 4: Reproducibility Tests of Single-pass Column Leaching with Acid Dose during Agglomeration and Low Acid Feed Flow The laterite ore used for these reproducibility tests was the blended composite ore with limonite/saprolite weight ratio of 1:1. Table 6 illustrates the chemical 15 composition of the composite ore. Table 6: Chemical Composition of Blended Laterite with Limonite/Saprolite Weight Ratio of 1:1 Al Co Cr Fe Mg Mn Ni Si Composite 3031 2.40 0.09 1.41 27.86 9.21 0.47 1.42 13.75 20 Concentrated sulfuric acid was used during agglomeration. The agglomerated laterite was charged into two columns with size of D x H = 25cm x 300 cm. With a single-pass style test, the blank sulfuric solution with constant acidity of 50 g/L was fed into column SC30 and SC31 to produce a PLS (pregnant leachate solution). The test conditions and results are listed in Table 7. 25 WO 2009/033227 PCT/AU2008/001357 -13 Table 7: Test Conditions and Results Column Operation Ore Agglomer- Irrigation Test Slump Acid Extraction % Style charge ation acid Flux Day % Consum Ni Co Fe (kg) dose (kg/t (L/m 2 /hr) -ption ore) (kg/t ore) SC30 Single 154 75 4 175 18 396 73 100 23 Pass SC31 Single 154 75 5 175 19 407 74 100 29 Pass Example 5: Column Leach tests with blended limonite/saprolite 5 composite ores Nos. 2 to 4 Three separate blended limonite/saprolite ore samples were subjected to column leach tests over a period of 10 months. The separate limonite/saprolite mineralogy, blended ore sample limonite/saprolite ratios, and 10 the blended ore sample chemistry are shown below in Table 8. Table 8 Column test Limonite Saprolite Limonite to Blended sample chemistry (%w/w) mineralogy mineralogy saprolite Ni Co Fe Mg Si Al blend ratio (solids mass basis) Composite 1 goethite 90% lizardite 73% 1:2 2.61 0.08 20.5 11.2 14.6 2.2 hematite 5% quartz 15% Composite 2 spinel 2% goethite 7% 1:2 2.22 0.08 20.2 12.4 14.3 2.4 dolomite 2% talc 4% Composite 3 quartz <1% spinel 1% 1:2 1.92 0.05 17.1 14.0 16.7 1.3 WO 2009/033227 PCT/AU2008/001357 -14 The column leach independent variables and dependent variables are shown below. This data in Table 9 describes the test conditions at the completion of leaching. 5 Table 9: test conditions at the completion of leaching. Independent variable Composite 2 Composite 3 Composite 4 Ore maximum size mm 25.0 25.0 25.0 Ore P 80 mm not determined 18.0 Ore Ni grade %w/w, dry basis 2.61 2.22 1.92 Agglomerate moisture %w/w 25.7 28.9 19.7 Agglomerate H 2
SO
4 rate kg/dry tonne 74.5 74.5 72.8 Agglomerate binder rate g/wet tonne 0 0 0 Agglomerate curing time hr 72 72 72 Agglomerate stack m 4.29 4.23 4.28 Column diameter m 0.075 0.075 0.075 Leach duration day 229 320 285 Lixiviant flux L/m 2 /hr 10.8 10.9 10.4 Cumulative lixiviant m 3 /dry tonne 15.8 17.5 15.0 Lixiviant [H 2
SO
4 ] g/L 50 50 50 dependent variable Composite 2 Composite 3 Composite 4 Extraction % Ni 76.9% 76.8% 78.1% Co 27.7% 54.3% 63.6% Fe 57.5% 54.3% 60.9% Mg 76.9% 71.0% 73.7% Extraction kg/t ore Ni 20.0 17.0 15.0 Co 0.23 0.44 0.33 Fe 118 102 104 Mg 86 88 103 Acid consumption kg/t ore 684 637 710 kg/kg Ni 35.5 37.6 47.9 Permeability (at end of L/m 2 /hr > 20 > 40 > 80 leach) The progressive nickel extraction graphs of blended ores Nos. 1 to 3 are shown in Figure 2.
Claims (19)
1. A process for the recovery of nickel and/or cobalt from a lateritic ore by heap leaching, the process including the steps of: 5 a) forming one or more heaps from a lateritic ore body wherein that lateritic ore body includes a blend of both limonitic and saprolitic type ores; b) leaching the one or more heaps with a leach solution; and c) recovering the nickel and/or cobalt from the resultant heap leachate. 10
2. A process according to claim 1 wherein the blend of limonitic and saprolitic type ores includes at least 15% to 85% wt of limonitic type ore and 15% to 85% wt saprolitic type ore. 15
3. A process according to claim 2 wherein the blend includes at least 40% to 60% wt of limonitic type ores and 40% to 60% wt of saprolitic type ores.
4. A process according to claim 1 wherein the one or more heaps include a 20 blend of limonitic and saprolitic type ores in the weight ratio range of from about 5:1 to 1:5.
5. A process according to claim 4 wherein the blend is in a weight ratio of about 1:1. 25
6. A process according to any one of the preceding claims wherein the overall silicon content in the blend of limonitic and saprolitic type ores is greater than 13% wt. 30
7. A process according to any one of the preceding claims where the overall silicon content in the blend of limonitic and saprolitic type ores is in the range from 15% to 40% wt. WO 2009/033227 PCT/AU2008/001357 -16
8. A process according to any one of the preceding claims wherein the overall quartz content in the blended limonitic and saprolitic type ores is greater than 28% wt. 5
9. A process according to claim 8 wherein the overall quartz content is within the range of from 32% to 86% wt.
10. A process according to any one of the preceding claims wherein the blend of limonitic and saprolitic type ore is predominantly transition zone 10 ore.
11. A process according to any one of claims 1 to 9 wherein the limonitic and saprolitic type ores are sourced separately from the limonite zone and the saprolite zone, or a combination of ores from each of the limonite, 15 saprolite and transition zones.
12. A process according to claim 1 wherein the leach solution is a mineral acid selected from the group consisting of hydrochloric acid, sulfuric acid and/or nitric acid. 20
13. A process according to claim 12 wherein the leach solution is avid supplemented fresh water, seawater or saline water.
14. A process according to claim 12 or 13 wherein the concentration of the 25 acid is sufficient to effect dissolution of nickel from the ore.
15. A process according to claim 13 wherein the concentration of the acid is at least about 0.10 molar. 30
16. A process according to claim 1 wherein the ore is pelletised or agglomerated prior to forming into the one or more heaps, by mixing the ore with concentrated sulfuric acid. WO 2009/033227 PCT/AU2008/001357 -17
17. A process according to any one of the preceding claims wherein a plurality of heaps is formed and arranged in at least a primary and a secondary heap, the process including the steps of: a) adding the leach solution to the secondary heap to produce an 5 intermediate product liquor; and b) adding the acidic intermediate product liquor to the primary heap to leach the primary heap in a counter current process, and producing a nickel and cobalt rich resultant heap leachate for further nickel and cobalt recovery. 10
18. A process according to claim 17 wherein the intermediate product liquor is separated into two portions; that portion having a pH of greater than 2 is removed and transferred downstream for nickel and/or cobalt recovery, while the portion with a pH of less than 2 is used for the leach solution for 15 the primary heap in the counter current system.
19. A process according to any one of the preceding claims wherein the nickel and cobalt recovery includes ion exchange (IX), solvent extraction (SX), electrowinning (EW), multi-stage neutralization to produce Ni/Co 20 hydroxides, pyrohydrolysis to produce Ni/Co oxides and sulfidation to produce Ni/Co sulfides
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2008299587A AU2008299587B2 (en) | 2007-09-13 | 2008-09-12 | Limonite and saprolite heap leach process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2007904992 | 2007-09-13 | ||
| AU2007904992A AU2007904992A0 (en) | 2007-09-13 | Limonite and Saprolite Heap Leach Process | |
| AU2008299587A AU2008299587B2 (en) | 2007-09-13 | 2008-09-12 | Limonite and saprolite heap leach process |
| PCT/AU2008/001357 WO2009033227A1 (en) | 2007-09-13 | 2008-09-12 | Limonite and saprolite heap leach process |
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| AU2008299587A1 true AU2008299587A1 (en) | 2009-03-19 |
| AU2008299587B2 AU2008299587B2 (en) | 2013-02-07 |
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| US (1) | US20100282024A1 (en) |
| CN (1) | CN101802234B (en) |
| AU (1) | AU2008299587B2 (en) |
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| WO (1) | WO2009033227A1 (en) |
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| CN101910428B (en) * | 2007-12-24 | 2012-05-16 | Bhp比利通Ssm开发有限公司 | Laterite heap leaching with ferrous lixiviants |
| US9624560B2 (en) * | 2010-06-15 | 2017-04-18 | Teck Resources Limited | Recovery of residual copper from heap leach residues |
| CN102191377A (en) * | 2011-05-06 | 2011-09-21 | 广西银亿科技矿冶有限公司 | Red clay nickel ore heap leaching method |
| US8597601B2 (en) * | 2011-06-03 | 2013-12-03 | Vale S.A. | Selective base metals leaching from laterite ores |
| CN103131855A (en) * | 2011-11-29 | 2013-06-05 | 沈阳有色金属研究院 | Method for treating normal pressure leaching of transitional nickel laterite ore |
| WO2014047672A1 (en) * | 2012-09-28 | 2014-04-03 | Direct Nickel Pty Ltd | Method for the recovery of metals from nickel bearing ores and concentrates |
| CN104805282A (en) * | 2014-01-28 | 2015-07-29 | 广西银亿科技矿冶有限公司 | Laterite nickel ore sulfuric acid curing heap leaching method |
| JP7556305B2 (en) * | 2021-02-16 | 2024-09-26 | 住友金属鉱山株式会社 | Apparatus and method for calculating composition of a substance |
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| US6261527B1 (en) * | 1999-11-03 | 2001-07-17 | Bhp Minerals International Inc. | Atmospheric leach process for the recovery of nickel and cobalt from limonite and saprolite ores |
| US6312500B1 (en) * | 2000-03-30 | 2001-11-06 | Bhp Minerals International Inc. | Heap leaching of nickel containing ore |
| AU2002951754A0 (en) * | 2002-10-01 | 2002-10-17 | European Nickel Plc | Heap leaching base metals from oxide ores |
| CL2004001045A1 (en) * | 2003-05-16 | 2005-06-03 | Jaguar Nickel Inc | PROCESS FOR LIXIVING LATERIC MINERAL NICKEL CONTAINING BASE OXIDES BASED USING A LIXIVIANT AT A pH LESS THAN 3, COMPOSED BY CHLORIDE ACID AND CHLORINE SALTS CONTAINING CATIONS WHERE CHLORINE CONCENTRATION IS GREATER |
| RU2346996C2 (en) * | 2004-06-29 | 2009-02-20 | ЮРОПИЭН НИКЕЛЬ ПиЭлСи | Improved leaching of base metals |
| KR20070060120A (en) * | 2004-09-17 | 2007-06-12 | 비에이치피 빌리톤 에스에스엠 테크놀로지 피티와이 엘티디 | Ferro-nickel or nickel mat production by a combination of wet metallurgy process and dry metallurgy process |
| DOP2006000048A (en) * | 2005-02-24 | 2006-08-31 | Bhp Billiton Ssm Dev Pty Ltd | PRODUCTION OF FERRONICKEL (FERRONIQUEL PRODUCTION) |
| WO2006119559A1 (en) * | 2005-05-13 | 2006-11-16 | Bhp Billiton Ssm Technology Pty Ltd | An improved process for heap leaching of nickeliferous oxidic ores |
| AU2006236085C1 (en) * | 2005-11-28 | 2014-02-27 | Vale S.A. | Process for extraction of nickel, cobalt, and other base metals from laterite ores by using heap leaching and product containing nickel, cobalt, and other metals from laterite ores |
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- 2008-09-12 AU AU2008299587A patent/AU2008299587B2/en not_active Ceased
- 2008-09-12 CN CN2008801068362A patent/CN101802234B/en not_active Expired - Fee Related
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| WO2009033227A1 (en) | 2009-03-19 |
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| US20100282024A1 (en) | 2010-11-11 |
| AU2008299587B2 (en) | 2013-02-07 |
| CN101802234A (en) | 2010-08-11 |
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